JP6564066B2 - Thermoelectric conversion module and heat conductive laminate, and method for manufacturing thermoelectric conversion module and method for manufacturing heat conductive laminate - Google Patents

Description

  The present invention relates to a thermoelectric conversion module with good productivity, a method for manufacturing the thermoelectric conversion module, and a heat conductive laminate used for the thermoelectric conversion module.

Thermoelectric conversion materials that can mutually convert thermal energy and electrical energy are used for thermoelectric conversion elements such as power generation elements and Peltier elements that generate electricity by heat.
The thermoelectric conversion element can convert heat energy directly into electric power, and has an advantage that a movable part is not required. For this reason, a thermoelectric conversion module (power generation device) formed by connecting a plurality of thermoelectric conversion elements is provided in a portion where heat is exhausted, such as an incinerator or various facilities in a factory, so that it is not necessary to incur operation costs and is simple. Can get power.

Thermoelectric conversion elements are usually used as thermoelectric conversion modules in which a plurality of thermoelectric conversion elements are connected in series. As the thermoelectric conversion module, a so-called π-type thermoelectric conversion module using a thermoelectric conversion material such as Bi-Te is known.
As an example, the π-type thermoelectric conversion module processes P-type and N-type thermoelectric conversion materials into blocks, and alternately arranges them on a substrate such as ceramics, and connects the arranged thermoelectric conversion materials in series. That is how it is made.

Such a π-type thermoelectric conversion module takes time and effort to process block-shaped thermoelectric conversion materials, arrangement of thermoelectric conversion materials, connection of thermoelectric conversion materials by electrodes, and the like.
In contrast, a thermoelectric conversion in which a thermoelectric conversion layer and electrodes are formed on a flexible insulating support (substrate) such as a resin film by a coating method such as printing or a vacuum film forming method such as vacuum deposition. Module has been reported.

  For example, Patent Document 1 includes a flexible insulating sheet in which a plurality of top portions protruding to the front surface side and a plurality of bottom portions protruding to the back surface side are formed by folding back into a bellows shape (wave shape), and It consists of a thermocouple having a first contact and a second contact provided on the insulating sheet, the first contact is disposed in the top adjacent portion adjacent to the top portion, and the second contact is disposed in the bottom adjacent portion adjacent to the bottom portion. A thermoelectric conversion module is described.

  Further, Patent Document 2 discloses a flexible base material that is folded back in an accordion shape (wave shape structure) in which a top portion and a bottom portion are alternately repeated, and a first bottom portion that is formed on the base material and is connected to the top portion and the top portion. A first thermoelectric conversion layer along the first inclined surface between the top and a second thermoelectric conversion layer along the second inclined surface between the top and the second bottom connected to the top. The first thermoelectric conversion layer and the second thermoelectric conversion layer have the same shape, the first thermoelectric conversion layer is on the top side and the first bottom side, and the second thermoelectric conversion layer is on the top side. Thermoelectric conversion modules each having a connection point with wiring are described on the second bottom side.

In a thermoelectric conversion module using such a resin film or the like as a support, thermoelectric conversion is performed by a coating method using an ink-like thermoelectric conversion material or electrode material, or a vacuum film formation method such as vacuum evaporation of the thermoelectric conversion material or electrode material. Conversion layers and electrodes can be formed.
Therefore, this thermoelectric conversion module is easy to manufacture and can be manufactured at a lower cost than a π-type thermoelectric conversion module using a block-shaped thermoelectric conversion material.
Moreover, since the electromotive force per thermoelectric conversion element is very small, the thermoelectric conversion module needs to connect several hundred or more thermoelectric conversion elements in series to increase the voltage and the amount of power generation. On the other hand, if it is a thermoelectric conversion module using a resin film etc. as a support body, formation of many thermoelectric conversion elements can be easily coped with by manufacture by printing etc.

JP 2005-328000 A International Publication No. 2013/114854

  Various methods are conceivable as a method for improving the performance such as the power generation amount of the flexible bellows-like thermoelectric conversion module.

For example, as shown in Patent Document 1 and Patent Document 2, a thermoelectric conversion module having a shape folded in a conventional bellows shape has an inclined surface of the bellows on which a thermoelectric conversion layer or the like is formed, and an inclined surface facing each other. It is in a separated state.
However, such a bellows-like thermoelectric conversion module can reduce the size, improve the heat transfer efficiency, improve the mounting density of the thermoelectric conversion elements, etc. It is advantageous that the bellows be closed as much as possible by compressing in the arrangement direction.
However, in the conventional bellows-like thermoelectric conversion module, when the bellows is closed, the electrodes come into contact with each other and short-circuit, and no power is generated at all. Therefore, combining an insulating member with a bellows-like thermoelectric conversion module is considered.

Moreover, it is known that the thermoelectric conversion module can increase the amount of power generation by increasing the temperature difference of the thermoelectric conversion layer by using a radiation fin or the like together.
Therefore, for the purpose of improving the amount of power generation, it is conceivable to combine a heat radiating member similar to a heat radiating fin with a bellows-shaped thermoelectric conversion module.

As described above, when an insulating member or a heat radiating member is combined with the bellows-like thermoelectric conversion module, the structure is stably maintained without dissociating the thermoelectric conversion module and the member, and good handling properties are required. The
Further, it is conceivable that a flexible bellows-like thermoelectric conversion module is mounted on a curved surface such as a cylindrical tube by taking advantage of flexibility. Therefore, the bellows-like thermoelectric conversion module preferably has flexibility even when an insulating member or a heat radiating member is combined.

  However, at present, such a flexible bellows-like thermoelectric conversion module is combined with an insulating member, a heat radiating member, and the like, and the stability, handleability, flexibility, etc. of a good configuration are satisfied. No thermoelectric conversion module is known.

  An object of the present invention is to solve such problems of the prior art, and by combining an insulating member, a heat radiating member, and the like with a flexible bellows-like thermoelectric conversion module, it has a better configuration. The object is to provide a thermoelectric conversion module having stability and handleability and good flexibility, a heat conductive laminate used for the thermoelectric conversion module, and a method for producing the same.

In order to achieve such an object, the thermoelectric conversion module of the present invention includes a support folded back in a bellows shape, and a plurality of thermoelectric conversion layers that are formed on at least one surface of the support and are separated from each other A module body having a connection electrode connecting adjacent thermoelectric conversion layers,
One or more bellows-like members folded in a bellows shape, which are provided to match the irregularities with the module body, and
A flexible line that penetrates the module main body and at least one bellows-like member through the inclined surface of the module main body by the bellows-like folding and the sloped surface of the at least one bellows-like member by folding. There is provided a thermoelectric conversion module characterized by having a member.

In such a thermoelectric conversion module of the present invention, the bellows-like member is preferably at least one selected from an insulating member, a heat radiating member, and a thermoelectric conversion member.
Moreover, it is preferable that an insulating member is provided so as to face the surface on which the thermoelectric conversion layer of the module body is formed.
Moreover, it is preferable that a heat radiating member is provided facing the surface of the insulating member opposite to the module body.
Moreover, it is preferable to have the flexible 2nd linear member which penetrates the inclined surface of an insulating member and the inclined surface of a heat radiating member, and penetrates an insulating member and a heat radiating member.
Moreover, it is preferable that an insulating member has a heat conductive layer on the surface of an insulating layer, and an insulating layer is provided toward the formation surface of the thermoelectric conversion layer of a module main body.
In addition, the thermoelectric conversion member connects the member support body folded in a bellows shape, a plurality of member thermoelectric conversion layers formed on at least one surface of the member support body, and the adjacent thermoelectric conversion layers. It is preferable to have a member connection electrode.
Further, the module body has a thermoelectric conversion layer only on one side of the support, and the thermoelectric conversion member has a member thermoelectric conversion layer only on one side of the member support. A thermoelectric conversion member provided with the member support facing the thermoelectric conversion layer, and a thermoelectric conversion member provided with the member thermoelectric conversion layer facing the support of the module main body. preferable.
Moreover, it is preferable to have a plurality of thermoelectric conversion members, and to have one or more combinations of thermoelectric conversion members provided to face the member support and the member thermoelectric conversion layer.
Moreover, it is preferable that a linear member penetrates places other than the formation position of a thermoelectric conversion layer and the formation position of a connection electrode of a module main body.
Moreover, it is preferable that a linear member penetrates the outer side of the longitudinal direction of a ridgeline at the same position in the inclination direction of an inclined surface with respect to a connection electrode.
Furthermore, it is preferable that the thermoelectric conversion layer of the module main body is a P-type thermoelectric conversion layer and an N-type thermoelectric conversion layer that are alternately provided on each inclined surface on one side of the support.

Further, the heat conductive laminate of the present invention is an insulating member folded back in a bellows shape,
A heat dissipating member folded in a bellows shape, provided with the insulating member and the unevenness; and
It has a flexible linear member that penetrates the insulating member and the heat radiating member through the inclined surface by the bellows-like folding of the insulating member and the inclined surface by the bellows-like folding of the heat radiating member. A thermally conductive laminate is provided.

  In such a heat conductive laminate of the present invention, the insulating member preferably has a heat conductive layer on the surface of the insulating layer.

The first aspect of the method for manufacturing a thermoelectric conversion module of the present invention includes a support folded back in a bellows shape, and a plurality of thermoelectric conversion layers that are formed on at least one surface of the support and are spaced apart from each other. A step of producing a module body having a connection electrode for connecting adjacent thermoelectric conversion layers and a flexible linear member that passes through the inclined surface of the bellows-like fold through the bellows;
A step of producing a bellows-like member having a flexible linear member that is folded back into a bellows shape and penetrates the inclined surface by the bellows-like folding;
The step of laminating the module main body and the bellows-like member together with the irregularities in the transport path changing portion provided in the transport path, while transporting the module main body and the bellows-like member in the direction orthogonal to the ridge line due to the bellows-like folding, and
Providing a flexible fixing linear member that penetrates the inclined surface of the module main body and the inclined surface of the bellows-like member and passes through the stacked module main body and the bellows-like member. A method for manufacturing a thermoelectric conversion module is provided.

In the first aspect of the method for manufacturing a thermoelectric conversion module of the present invention, the fixing linear member is at least one of a linear member that passes through the module main body and a linear member that passes through the bellows-like member, In the step of inserting the fixing linear member, the step of pulling out the linear member from the laminated module main body and the bellows-like member, the step of aligning the module main body and the bellows-like member, and the slope from which the linear member is removed Preferably, a step of inserting at least one of the linear member extracted from the module main body and the linear member extracted from the bellows-like member into the through hole is performed.
In the step of inserting the linear member for fixing, the linear member for inserting the module main body and the linear member for inserting the bellows-like member are left as they are, and the linear member for fixing is attached to the module main body and the bellows-like member. It is preferable to insert.
Moreover, it is preferable that the bellows-like member is one or more selected from an insulating member, a heat dissipation member, and a thermoelectric conversion member.
Further, the insulating member and the heat radiating member are laminated so as to be uneven, and the insulating member and the heat radiating member are inserted through the inclined surface of the insulating member and the inclined surface of the heat radiating member. It is preferable to provide a member.
Furthermore, it is preferable that the insulating member has a heat conductive layer on the surface of the insulating layer.

Further, the second aspect of the method for manufacturing a thermoelectric conversion module of the present invention is to connect a support, a plurality of thermoelectric conversion layers formed on at least one surface of the support, and an adjacent thermoelectric conversion layer. A step of laminating a plurality of sheet-like materials having connection electrodes,
A step of folding the laminate of sheet-like materials into a bellows shape; and
There is provided a method for manufacturing a thermoelectric conversion module, comprising: a step of inserting a flexible linear member through an inclined surface formed by a bellows-like folding of a sheet-like material folded in a bellows shape. .

Furthermore, the manufacturing method of the heat conductive laminated body of the present invention produces an insulating member having a flexible linear member that is folded in a bellows shape and penetrates the bellows through an inclined surface by the bellows-like folding. The process of
A step of producing a heat dissipating member having a flexible linear member that is folded into a bellows shape and penetrates the inclined surface by the bellows-like folding;
A process of laminating the insulating member and the heat dissipation member together with the unevenness in the change portion of the transport path provided in the transport path while transporting the insulating member and the heat dissipation member in a direction orthogonal to the ridge line by the bellows-like folding. And
There is provided a method for manufacturing a thermally conductive laminate, comprising a step of inserting a flexible fixing linear member through an inclined surface of a laminated insulating member and a heat dissipation member.

In such a method for producing a thermally conductive laminate of the present invention, the fixing linear member is at least one of a linear member that passes through the inclined surface of the insulating member and a linear member that passes through the inclined surface of the heat dissipation member. Yes, in the step of inserting the fixing linear member, the step of pulling out the linear member from the laminated insulating member and the heat radiating member, the step of aligning the insulating member and the heat radiating member, and the slope from which the linear member is removed The step of inserting at least one of the linear member extracted from the insulating member and the linear member extracted from the heat radiating member into the through hole is preferably performed.
Further, in the step of inserting the fixing linear member, the linear member for inserting the insulating member and the linear member for inserting the heat dissipating member are left as they are, and the fixing linear member is inserted into the insulating member and the heat dissipating member. Is preferred.
Furthermore, it is preferable that the insulating member has a heat conductive layer on the surface of the insulating layer.

  According to the present invention, the flexible bellows-shaped thermoelectric conversion module is combined with an insulating member, a heat radiating member, and the like, and further, has a stable configuration and handleability, and is flexible. A good thermoelectric conversion module can be obtained.

FIG. 1A is a schematic front view of an example of the thermoelectric conversion module of the present invention. FIG. 1B is a schematic perspective view of the thermoelectric conversion module shown in FIG. 1A. FIG. 1C is a schematic front view showing a state in which the bellows of the thermoelectric conversion module shown in FIG. 1A is closed. FIG. 2 is a conceptual diagram for explaining the thermoelectric conversion module shown in FIG. 1. FIG. 3 is a schematic front view of another example of the thermoelectric conversion module of the present invention. FIG. 4A is a schematic front view of another example of the thermoelectric conversion module of the present invention. FIG. 4B is a schematic front view illustrating a state in which the bellows of the thermoelectric conversion module illustrated in FIG. 4A is closed. FIG. 5 is a schematic front view of another example of the thermoelectric conversion module of the present invention. FIG. 6 is a schematic front view of another example of the thermoelectric conversion module of the present invention. FIG. 7 is a conceptual diagram for explaining another example of the thermoelectric conversion module of the present invention. FIG. 8 is a schematic front view of another example of the thermoelectric conversion module of the present invention. FIG. 9 is a schematic front view of another example of the thermoelectric conversion module of the present invention. FIG. 10 is a conceptual diagram for explaining another example of the thermoelectric conversion module of the present invention. FIG. 11 is a conceptual diagram for explaining another example of the thermoelectric conversion module of the present invention. FIG. 12 is a schematic front view of an example of the thermally conductive laminate of the present invention. FIG. 13: is a schematic front view for demonstrating an example of the 1st aspect of the manufacturing method of the thermoelectric conversion module of this invention. FIG. 14 is a conceptual diagram for explaining an example of the first aspect of the method for manufacturing a thermoelectric conversion module of the present invention. FIG. 15A is a schematic front view for explaining an example of the first aspect of the manufacturing method of the thermoelectric conversion module of the present invention. FIG. 15B is a schematic front view for explaining an example of the first aspect of the method for producing the thermoelectric conversion module of the present invention. FIG. 16A is a schematic front view for explaining an example of the first aspect of the manufacturing method of the thermoelectric conversion module of the present invention. FIG. 16B is a schematic front view for explaining an example of the first aspect of the method for producing the thermoelectric conversion module of the present invention. FIG. 17A is a schematic front view for explaining an example of a second aspect of the method for manufacturing a thermoelectric conversion module of the present invention. FIG. 17B is a schematic front view for explaining an example of the second aspect of the method for manufacturing the thermoelectric conversion module of the present invention. FIG. 17C is a schematic front view for explaining an example of the second aspect of the method for manufacturing the thermoelectric conversion module of the present invention.

Hereinafter, the thermoelectric conversion module and the thermally conductive laminate of the present invention, and the method of manufacturing the thermoelectric conversion module and the method of manufacturing the thermally conductive laminate will be described in detail based on preferred embodiments shown in the accompanying drawings. .
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In FIG. 1A-FIG. 1C, an example of the thermoelectric conversion module of this invention is shown notionally.
1A is a schematic front view, FIG. 1B is a schematic perspective view, and FIG. 1C is a schematic front view showing a state in which the bellows of the thermoelectric conversion module 10 is closed.

In addition, a front view is the figure which looked at the thermoelectric conversion module 10 of this invention in the surface direction of the module main body 11. FIG.
Further, in FIG. 1C, the bellows-like folded portion is shown in a rectangular shape so that the configuration and each member of the thermoelectric conversion module 10 can be clearly shown. However, in the thermoelectric conversion module 10 of the present invention, the state where the bellows is closed is a state in which the thermoelectric conversion module 10 shown in FIG. 1A is compressed in the lateral direction in the drawing. Therefore, in the state where the bellows of the thermoelectric conversion module 10 is closed, the fold-back portion that has been folded and valley-folded as described later has an acute angle. This also applies to FIG. 4B described later.

As shown in FIGS. 1A to 1C, the thermoelectric conversion module 10 of the present invention includes a module body 11, an insulating member 20, and a wire 24. In FIG. 1B, in order to clearly show the configuration, the insulating member 20 is indicated by a two-dot chain line.
The thermoelectric conversion module 10 includes a module main body 11 folded in a bellows shape and an insulating member 20 folded in a bellows shape so that the concave and convex portions are laminated, and the module main body 11, the bellows shaped insulating member 20 and both It has a configuration in which the wire 24 is inserted. In the following description, “thermoelectric conversion module 10” is also referred to as “module 10”.

In the present invention, the term “laminated” refers to a state in which the concave and convex portions of the bellows, that is, the mountain fold portion and the valley fold portion, are combined and the convex portions are inserted into the respective concave portions facing the maximum surface. This includes not only a state in which the opposing surfaces are in full contact, but also a state in which some or all of the opposing surfaces of the stacked bellows are held apart from each other.
Therefore, in the example shown in FIG. 1A, the module main body 11 and the insulating member 20 are entirely separated from each other. For example, in a stacked state, the module main body 11 and the insulating member 20 protrude upward in the drawing. The state which the surface which opposes may contact in the top part of a part may be sufficient. Alternatively, the module body 11 and the insulating member 20 may be stacked, and the entire surface of the insulating member 20 may be in contact with the opposing surface of the module body 11.

In FIG. 2, the conceptual diagram which extended the module main body 11 in planar shape is shown.
As shown in FIGS. 1A and 2, the module main body 11 includes a support 12, a P-type thermoelectric conversion layer 14 p, an N-type thermoelectric conversion layer 16 n, and a connection electrode 18.
In FIG. 1A and FIG. 1C, the support 12 is hatched to clearly show the configuration, and the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n are shaded. The same applies to FIG. 2 (FIGS. 10 and 11 to be described later) regarding the shading of the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n.

As shown in FIG. 2, the module main body 11 is formed with connection electrodes 18 having a fixed length at regular intervals in the longitudinal direction of the support 12 on one surface of the long support 12. On the surface, P-type thermoelectric conversion layers 14p and N-type thermoelectric conversion layers 16n having a predetermined length at regular intervals in the longitudinal direction of the support 12 are alternately formed.
In the following description, the “longitudinal direction of the support 12” is also referred to as “longitudinal direction”. In the following description, the width direction of the support 12, that is, the direction orthogonal to the longitudinal direction is also referred to as “width direction”. Accordingly, the width direction is a direction perpendicular to the paper surface in FIGS. 1A and 1C.
In the present invention, the length and interval in the longitudinal direction are the length and interval in a state where the module main body 11 is extended in a planar shape.

The module body 11 has a bellows-like shape that is alternately folded back into a mountain fold and a valley fold by a fold line parallel to the width direction of the support 12 at the center in the longitudinal direction of the connection electrode 18. Accordingly, the module main body 11 alternately has mountain folds and valley folds in the longitudinal direction and has top and bottom alternately by bellows-like folding. Therefore, the longitudinal direction coincides with the inclination direction of the inclined surface by the bellows-like folding.
In this example, the support 12 is folded inward on the inner side, that is, the side on which the connection electrode 18 is convex, and the outer side, ie, on the side in which the connection electrode 18 is concave, is valley-folded. . That is, the upper side in FIG. 1A is the mountain fold side, and the lower side is the valley fold side.

The module body 11 includes a P-type thermoelectric conversion layer 14p and an N-type thermoelectric conversion layer 16n that are adjacent to each other in the longitudinal direction, with the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n arranged alternately in the longitudinal direction. Are connected in series by the connection electrode 18.
Further, as described above, the module main body 11 is folded in a mountain fold and a valley fold at the longitudinal center of the connection electrode 18 to have a bellows shape.
Such a module main body 11 generates heat by providing a high temperature heat source on the lower side of FIG. 1A and heat radiating means such as heat radiating fins on the upper side, and generating a temperature difference in the vertical direction in FIG. 1A. . In other words, the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n formed on the inclined surface of the support 12 generate electricity by causing a temperature difference in the thermoelectric conversion layer in the longitudinal direction.

The support (substrate) 12 is long, flexible, and insulative.
In the module of the present invention, if the support 12 has flexibility and insulating properties, it is a long sheet-like material (film) used in a known thermoelectric conversion module using a flexible support. However, various types are available.
Specifically, polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-phthalenedicarboxylate, polyimide, Examples of the sheet-like material are polycarbonate, polypropylene, polyethersulfone, cycloolefin polymer, polyetheretherketone (PEEK), triacetylcellulose (TAC), and other resins, glass epoxy, liquid crystalline polyester, and the like.
Especially, the sheet-like material which consists of a polyimide, a polyethylene terephthalate, a polyethylene naphthalate etc. is utilized suitably by points, such as thermal conductivity, heat resistance, solvent resistance, availability, and economical efficiency.

The thickness of the support 12 may be set as appropriate so that sufficient flexibility can be obtained and the thickness that functions as the support 12 can be set according to the material for forming the support 12.
Note that the length and width of the support 12 may be appropriately set according to the size and use of the module body 11.

A through hole 28 is formed in the inclined surface by folding in the vicinity of both ends in the width direction of the support 12. Specifically, as a preferable aspect, the through hole 28 is arranged in the width direction outside the region where the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n in the width direction of the support 12 and the connection electrode 18 are formed. Located in. Further, the through hole 28 is symmetrical with respect to the center of the connection electrode 18 in the longitudinal direction, that is, the fold-back line of the mountain fold shown by a one-dot chain line in FIG. A pair is formed at the position. As described above, the longitudinal direction and the inclined direction of the inclined surface are the same direction.
Further, the through hole 28 is preferably formed at a position that is linear in the longitudinal direction when the support 12 is folded back in a bellows shape. That is, the through hole 28 is preferably formed at a position where a single straight line that is long in the longitudinal direction can be inserted when the support 12 is folded in a bellows shape.

As will be described later, the wire 24 penetrates the module main body 11 and the insulating member 20 through the through hole 28.
In addition, the code | symbol 28a is a reinforcement member for reinforcing the through-hole 28 provided as needed. The reinforcing member 28a may be formed using a known hole reinforcing member such as a metal or a resin material.

On one surface of the support 12, P-type thermoelectric conversion layers 14 p and N-type thermoelectric conversion layers 16 n having a certain length are alternately arranged at regular intervals in the longitudinal direction.
In the following description, when it is not necessary to distinguish between the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n, both are collectively referred to as a “thermoelectric conversion layer”.

In the module main body 11 of the present invention, various types of P-type thermoelectric conversion layers 14p and N-type thermoelectric conversion layers 16n made of known thermoelectric conversion materials can be used.
Examples of the thermoelectric conversion material forming the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n include nickel or a nickel alloy.
Various nickel alloys that generate electricity by generating a temperature difference can be used. Specific examples include nickel alloys mixed with one component or two or more components such as vanadium, chromium, silicon, aluminum, titanium, molybdenum, manganese, zinc, tin, copper, cobalt, iron, magnesium, and zirconium. The
When nickel or a nickel alloy is used for the P-type thermoelectric conversion layer 14p or the N-type thermoelectric conversion layer 16n, the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n have a nickel content of 90 atomic% or more. Preferably, the nickel content is more preferably 95 atomic% or more, and particularly preferably made of nickel. The P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n made of nickel include those having inevitable impurities.

When a nickel alloy is used as the thermoelectric conversion material of the P-type thermoelectric conversion layer 14p, chromel containing nickel and chromium as main components is typical. In the case where a nickel alloy is used as the thermoelectric material of the N-type thermoelectric conversion layer 16n, constantan mainly composed of copper and nickel is typical.
When nickel or a nickel alloy is used as the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n, and when nickel or a nickel alloy is also used as the connection electrode 18, the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n and the connection electrode 18 may be integrally formed.

Examples of thermoelectric conversion materials that can be used for the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n include the following materials in addition to nickel and nickel alloys. The material composition is shown in parentheses.
BiTe system (BiTe, SbTe, BiSe and their compounds), PbTe system (PbTe, SnTe, AgSbTe, GeTe and their compounds), Si-Ge system (Si, Ge, SiGe), Silicide system (FeSi, MnSi, CrSi) ), A skutterudite system (MX ₃ or RM ₄ X ₁₂ , where M = Co, Rh, Ir represents, X = As, P, Sb, R = La, Yb, Ce Transition metal oxides (NaCoO, CaCoO, ZnInO, SrTiO, BiSrCoO, PbSrCoO, CaBiCoO, BaBiCoO), zinc antimony (ZnSb), boron compounds (CeB, BaB, SrB, CaB, MgB, VB, NiB) , CuB, LiB), cluster solid (B cluster, Si class) Chromatography, C cluster, AlRe, AlReSi), and the like zinc oxide based (ZnO).

As the thermoelectric conversion material used for the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n, a material that can be pasted so that a film can be formed by coating or printing can be used.
Specific examples of such thermoelectric conversion materials include organic thermoelectric conversion materials such as conductive polymers or conductive nanocarbon materials.
Examples of the conductive polymer include a polymer compound having a conjugated molecular structure (conjugated polymer). Specific examples include known π-conjugated polymers such as polyaniline, polyphenylene vinylene, polypyrrole, polythiophene, polyfluorene, acetylene, and polyphenylene. In particular, polydioxythiophene can be preferably used.
Specific examples of the conductive nanocarbon material include carbon nanotubes, carbon nanofibers, graphite, graphene, and carbon nanoparticles. These may be used alone or in combination of two or more. Among these, carbon nanotubes are preferably used because of the better thermoelectric properties. In the following description, “carbon nanotube” is also referred to as “CNT”.

CNT is a single-layer CNT in which one carbon film (graphene sheet) is wound in a cylindrical shape, two-layer CNT in which two graphene sheets are concentrically wound, and a plurality of graphene sheets in a concentric circle There are multi-walled CNTs wound in a shape. In the present invention, single-walled CNTs, double-walled CNTs, and multilayered CNTs may be used alone, or two or more kinds may be used in combination. In particular, single-walled CNT and double-walled CNT having excellent properties in terms of conductivity and semiconductor properties are preferably used, and single-walled CNT is more preferably used.
Single-walled CNTs may be semiconducting or metallic, and both may be used in combination. When using both semiconducting CNT and metallic CNT, the content ratio of both can be adjusted suitably. The CNT may contain a metal or the like, or may contain a molecule such as fullerene.

The average length of the CNT is not particularly limited and can be selected as appropriate. Specifically, although it depends on the distance between the electrodes, the average length of the CNT is preferably 0.01 to 2000 μm, more preferably 0.1 to 1000 μm from the viewpoints of manufacturability, film formability, conductivity, and the like. 1 to 1000 μm is particularly preferable.
The diameter of the CNT is not particularly limited, but is preferably 0.4 to 100 nm, more preferably 50 nm or less, and particularly preferably 15 nm or less from the viewpoints of durability, transparency, film formability, conductivity, and the like. In particular, when single-walled CNT is used, the diameter of the CNT is preferably 0.5 to 2.2 nm, more preferably 1.0 to 2.2 nm, and particularly preferably 1.5 to 2.0 nm.
CNT may contain defective CNT. Such CNT defects are preferably reduced in order to reduce the conductivity of the thermoelectric conversion layer. The amount of CNT defects can be estimated by the ratio G / D of the G-band and D-band of the Raman spectrum. It can be estimated that the higher the G / D ratio, the less the amount of defects, the CNT material. The CNT preferably has a G / D ratio of 10 or more, more preferably 30 or more.

Also, CNTs modified or treated with CNTs can be used. Modification or treatment methods include a method of encapsulating a ferrocene derivative or nitrogen-substituted fullerene (azafullerene), a method of doping an alkali metal (such as potassium) or a metal element (such as indium) into the CNT by an ion doping method, CNT in a vacuum The method etc. which heat this are illustrated.
When CNT is used, in addition to single-walled CNT and multi-walled CNT, nanocarbon such as carbon nanohorn, carbon nanocoil, carbon nanobead, graphite, graphene, and amorphous carbon may be included.

When CNT is used for the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n, the thermoelectric conversion layer preferably contains a P-type dopant or an N-type dopant.
(P-type dopant)
P-type dopants include halogens (iodine, bromine, etc.), Lewis acids (PF ₅ , AsF _5, etc.), proton acids (hydrochloric acid, sulfuric acid, etc.), transition metal halides (FeCl ₃ , SnCl ₄ etc.), metal oxides (Molybdenum oxide, vanadium oxide, etc.), organic electron accepting substances and the like are exemplified. Examples of organic electron accepting substances include 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-dimethyl-7,7,8,8- Tetracyanoquinodimethane such as tetracyanoquinodimethane, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane (TCNQ) derivatives, 2,3-dichloro-5,6-dicyano-p-benzoquinone, benzoquinone derivatives such as tetrafluoro-1,4-benzoquinone, etc., 5,8H-5,8-bis (dicyanomethylene) quinoxaline, A suitable example is dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile.
Among them, organic electron-accepting substances such as TCNQ (tetracyanoquinodimethane) derivatives or benzoquinone derivatives are preferably exemplified in terms of material stability, compatibility with CNTs, and the like.
Any of the P-type dopant and the N-type dopant may be used alone or in combination of two or more.

(N-type dopant)
Known N-type dopants include (1) alkali metals such as sodium and potassium, (2) phosphines such as triphenylphosphine and ethylenebis (diphenylphosphine), and (3) polymers such as polyvinylpyrrolidone and polyethyleneimine. These materials can be used.
Also, for example, polyethylene glycol type higher alcohol ethylene oxide adducts, ethylene oxide adducts such as phenol or naphthol, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acids Amide ethylene oxide adduct, fat ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, etc., or polyhydric alcohol type glycerol Fatty acid ester, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan Fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines. Also, acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based and silicone-based surfactants can be used in the same manner.

As the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n, a thermoelectric conversion layer in which a thermoelectric conversion material is dispersed in a resin material (binder) is also preferably used.
Especially, the thermoelectric conversion layer formed by disperse | distributing a conductive nano carbon material to a resin material is illustrated more suitably. Among these, a thermoelectric conversion layer in which CNT is dispersed in a resin material is particularly preferably exemplified in that high conductivity is obtained.
Various known non-conductive resin materials (polymer materials) can be used as the resin material.
Specific examples include vinyl compounds, (meth) acrylate compounds, carbonate compounds, ester compounds, epoxy compounds, siloxane compounds, and gelatin.

  More specifically, examples of the vinyl compound include polystyrene, polyvinyl naphthalene, polyvinyl acetate, polyvinyl phenol, and polyvinyl butyral. Examples of the (meth) acrylate compound include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyphenoxy (poly) ethylene glycol (meth) acrylate, polybenzyl (meth) acrylate and the like. Examples of the carbonate compound include bisphenol Z-type polycarbonate and bisphenol C-type polycarbonate. As the ester compound, amorphous polyester is exemplified.

Preferred examples include polystyrene, polyvinyl butyral, (meth) acrylate compounds, carbonate compounds, and ester compounds, and more preferred are polyvinyl butyral, polyphenoxy (poly) ethylene glycol (meth) acrylate, polybenzyl (meth) acrylate, and amorphous. An example is a reactive polyester.
In the thermoelectric conversion layer in which the thermoelectric conversion material is dispersed in the resin material, the quantity ratio of the resin material to the thermoelectric conversion material is the material used, the required thermoelectric conversion efficiency, the viscosity or solid content concentration of the solution affecting printing, etc. It may be set appropriately according to the above.

Further, when CNT is used for the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n, a thermoelectric conversion layer mainly composed of CNT and a surfactant is also preferably used.
By constituting the thermoelectric conversion layer with CNT and a surfactant, the thermoelectric conversion layer can be formed with a coating composition to which a surfactant is added. Therefore, the thermoelectric conversion layer can be formed with a coating composition in which CNTs are reasonably dispersed. As a result, good thermoelectric conversion performance can be obtained by the thermoelectric conversion layer containing many CNTs that are long and have few defects.

As the surfactant, a known surfactant can be used as long as it has a function of dispersing CNTs. More specifically, various surfactants can be used as long as they have a group that dissolves in water, a polar solvent, or a mixture of water and a polar solvent and adsorbs CNTs.
Accordingly, the surfactant may be ionic or nonionic. The ionic surfactant may be any of cationic, anionic and amphoteric.
Examples of the anionic surfactant include alkylbenzene sulfonates such as dodecylbenzene sulfonic acid, aromatic sulfonic acid surfactants such as dodecyl phenyl ether sulfonate, monosoap anionic surfactants, ether sulfates Surfactants, phosphate surfactants and carboxylic acid surfactants such as sodium deoxycholate or sodium cholate, carboxymethylcellulose and salts thereof (sodium salt, ammonium salt, etc.), ammonium polystyrene sulfonate, Examples thereof include water-soluble polymers such as polystyrene sulfonate sodium salt.

Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts. Examples of amphoteric surfactants include alkyl betaine surfactants and amine oxide surfactants.
In addition, examples of nonionic surfactants include sugar ester surfactants such as sorbitan fatty acid esters, fatty acid ester surfactants such as polyoxyethylene resin acid esters, ether surfactants such as polyoxyethylene alkyl ether, and the like. Is exemplified.
Among these, ionic surfactants are preferably used, and among them, cholate or deoxycholate is preferably used.

In the thermoelectric conversion layer having CNT and a surfactant, the surfactant / CNT mass ratio is preferably 5 or less, and more preferably 3 or less.
Setting the mass ratio of surfactant / CNT to 5 or less is preferable in that higher thermoelectric conversion performance can be obtained.

Incidentally, the thermoelectric conversion layer made of an organic material, _{optionally, SiO 2, TiO 2, Al} 2 O 3, may have an inorganic material such as ZrO _2.
In addition, when a thermoelectric conversion layer contains an inorganic material, it is preferable that the content is 20 mass% or less, and it is more preferable that it is 10 mass% or less.

Such a P-type thermoelectric conversion layer 14p and an N-type thermoelectric conversion layer 16n may be formed by a known method. The following method is illustrated as an example.
First, a coating composition for forming a thermoelectric conversion layer containing a thermoelectric conversion material and necessary components such as a surfactant is prepared.
Subsequently, the coating composition used as the thermoelectric conversion layer prepared is patterned and apply | coated according to the thermoelectric conversion layer to form. The coating composition may be applied by a known method such as a method using a mask or a printing method.
After applying the coating composition, the coating composition is dried by a method according to the resin material to form a thermoelectric conversion layer. In addition, after drying a coating composition as needed, you may cure the coating composition (resin material) by ultraviolet irradiation etc.
Further, the thermoelectric conversion layer may be patterned by etching or the like after coating the prepared coating composition to be the thermoelectric conversion layer on the entire surface of the insulating support and drying it.

In the case of forming a thermoelectric conversion layer mainly composed of CNT and a surfactant, after forming the thermoelectric conversion layer with a coating composition, the thermoelectric conversion layer is immersed in a solvent that dissolves the surfactant, Alternatively, the thermoelectric conversion layer is preferably formed by washing the thermoelectric conversion layer with a solvent that dissolves the surfactant and then drying.
Thereby, the surfactant is removed from the thermoelectric conversion layer, and a thermoelectric conversion layer in which the surfactant / CNT mass ratio is extremely small, more preferably no surfactant is present, can be formed. The thermoelectric conversion layer is preferably patterned by printing.

As the printing method, various known printing methods such as screen printing, metal mask printing, and inkjet can be used. In addition, when pattern-forming a thermoelectric conversion layer using the coating composition containing CNT, it is more preferable to use metal mask printing.
The printing conditions may be appropriately set depending on the physical properties (solid content concentration, viscosity, viscoelastic physical properties) of the coating composition to be used, the opening size of the printing plate, the number of openings, the opening shape, the printing area, and the like.

  In addition, when forming P type thermoelectric conversion layer 14p and N type thermoelectric conversion layer 16n with inorganic materials, such as the above-mentioned nickel, nickel alloy, BiTe type material, etc. other than the formation method using such a coating composition. Alternatively, the thermoelectric conversion layer can be formed by using a film forming method such as sputtering, CVD (Chemical Vapor Deposition), vapor deposition, plating, or aerosol deposition.

The sizes of the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n may be set as appropriate according to the size of the module body 11, the width of the support 12, the size of the connection electrode 18, and the like. In the present invention, the size is the size in the surface direction of the support 12.
As described above, the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n have the same length in the longitudinal direction. Further, since the thermoelectric conversion layers are formed at regular intervals, the P-type thermoelectric conversion layers 14p and the N-type thermoelectric conversion layers 16n are alternately formed at the same intervals.

The thicknesses of the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n may be appropriately set according to the material for forming the thermoelectric conversion layer, but are preferably 1 to 20 μm, and more preferably 3 to 15 μm.
By setting the thicknesses of the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n within the above ranges, it is preferable in terms of obtaining good electrical conductivity and good printability.
The P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n may be the same or different in thickness, but basically have the same thickness.

In the module body 11, connection electrodes 18 are formed on the formation surfaces of the P-type thermoelectric conversion layer 14 p and the N-type thermoelectric conversion layer 16 n of the support 12.
The connection electrode 18 electrically connects the P-type thermoelectric conversion layers 14p and the N-type thermoelectric conversion layers 16n alternately formed in the longitudinal direction in series. As described above, in the illustrated example, the thermoelectric conversion layer is formed with a certain length in the longitudinal direction at regular intervals. Accordingly, the connection electrodes 18 having a certain length are formed at regular intervals. Further, the module body 11 is folded back at the center in the longitudinal direction of the connection electrode 18 by a mountain fold and a valley fold along a fold line parallel to the width direction.

Any material can be used for the connection electrode 18 as long as it has a necessary conductivity.
Specifically, various materials such as copper, silver, gold, platinum, nickel, aluminum, constantan, chromium, indium, iron, copper alloy, and other devices such as indium tin oxide (ITO) and zinc oxide (ZnO) Examples include materials used as transparent electrodes. Among these, copper, gold, silver, platinum, nickel, copper alloy, aluminum, constantan and the like are preferably exemplified, and copper, gold, silver, platinum and nickel are more preferably exemplified.
Further, the connection electrode 18 may be a laminated electrode such as a configuration in which a copper layer is formed on a chromium layer.

  The connection electrode 18 may be patterned by a known method according to the material for forming the connection electrode 18, such as a vapor deposition method such as vacuum deposition or sputtering, or a coating method such as printing.

The size of the connection electrode 18 may be set as appropriate according to the size of the module body 11, the width of the support 12, the sizes of the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n, and the like.
In addition, the thickness of the connection electrode 18 may be appropriately set according to the forming material so that the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n can ensure sufficient conductivity.

Such a module main body 11 can be produced by a known method.
As an example, the thermoelectric conversion layer and the connection electrode 18 are formed by patterning the long plate-like support 12 by a known method according to the forming material, and the outer side of the connection electrode 18 in the width direction, etc. A through hole 28 or further a reinforcing member 28a is formed at a position corresponding to the connection electrode 18 that is folded in the longitudinal direction. Thereafter, a known sheet-like material is bent, such as press working or processing with a roller having protrusions, and folded into a bellows shape to obtain a bellows-like module body 11.
These operations are preferably performed by so-called roll-to-roll, in which various processes are continuously performed while the support 12 (substrate to be processed) is conveyed in the longitudinal direction.

As described above, the module 10 has a configuration in which the module main body 11 and the insulating member 20 are stacked and the wire 24 is inserted through both of them. The insulating member 20 is a kind of bellows-like member in the present invention.
The insulating member 20 is formed by forming a heat conductive layer 32 on one surface of a long support 30 (insulating layer) having insulating properties and flexibility. It is a bellows shape that is alternately folded by valley folds. In this example, when the insulating member 20 is folded back, the support 30 is folded inward on the side where the heat conductive layer 32 is convex, and the support 12 is outside on the side where the heat conductive layer 32 is concave. The valley fold.
The insulating member 20 is laminated on the module body 11 with the support 30 facing the connection electrode 18 of the module body 11 and the surface on which the thermoelectric conversion layer is formed, with unevenness.

As the support 30, various kinds of sheet-like materials having insulating properties and flexibility can be used. Specifically, the sheet-like material exemplified in the module main body 11 is exemplified.
The width of the support 30, that is, the insulating member 20 may be appropriately set according to the width of the module body 11. Further, the length of the support 30 may be appropriately set according to the length of the module main body 11 and the height of the irregularities of the module main body 11 and the insulating member 20.
The thickness of the support 30 may be set as appropriate according to the size of the module 10 and the like so that sufficient insulation can be ensured and the support 30 can act as a support for the heat conductive layer 32.

The heat conductive layer 32 is a layer formed of a material having high heat conductivity. In the module 10 of the illustrated example, the insulating member 20 has the heat conductive layer 32 as a preferred embodiment.
Therefore, the insulating member 20 does not necessarily need to have the heat conductive layer 32, and the insulating member 20 may be configured with only the insulating support 30.
However, since the insulating member 20 has the heat conductive layer 32, the insulating member 20 also acts as a heat radiating member. Therefore, the temperature difference of the thermoelectric conversion layer can be increased to improve the amount of power generation. Furthermore, the bellows shape of the insulating member 20 can be suitably maintained by forming the heat conductive layer 32 with a metal material or the like.

As a material for forming the heat conductive layer 32, various materials used for so-called heat radiation fins can be used. Specific examples include various metal materials such as copper and aluminum, inorganic compounds such as alumina, boron nitride, and aluminum nitride, and carbon materials such as graphite. Among these, metal materials such as copper and aluminum are preferably used.
The thickness of the heat conductive layer 32 is set as appropriate according to the material for forming the heat conductive layer 32, the size of the unevenness of the insulating member 20, and the like to obtain the necessary heat conductivity, that is, the heat dissipation effect. do it.
Similar to the connection electrode 18, the heat conductive layer 32 may be formed by a known method such as a vacuum film formation method such as vacuum deposition or a coating method such as printing, depending on the forming material.

Also in such an insulating member 20, through holes 36 are formed in the vicinity of both end portions in the width direction of the inclined surface due to bellows-like folding.
Specifically, the through hole 36 of the insulating member 20 is formed at the same position as the through hole 28 of the module body 11 in the width direction. Further, in the longitudinal direction, a pair is formed at the valley fold portion at positions symmetrical to the folding line of the valley fold.
Similar to the through hole 28 of the module body 11, the through hole 36 is preferably formed at a position that is linear in the longitudinal direction when the insulating member 20 is folded back in a bellows shape. Further, the through hole 36 is preferably formed so that the through hole 28 of the module body 11 is also linear when the insulating member 20 is stacked on the module body 11.

The insulating member 20 can also be produced by a known method, like the module body 11 described above.
As an example, the heat conductive layer 32 is formed on the entire surface of the flat plate-like long support 30 by a known method according to the forming material, and the through hole 34 is formed at a predetermined position of the support 30. .
Thereafter, a known sheet-like material is bent, such as press working or processing with a roller having protrusions, and folded into a bellows shape, thereby forming the bellows-like insulating member 20.
These operations are preferably performed in a roll-to-roll manner as in the module body 11. Moreover, you may produce the insulating member 20 using the commercial item which has formed the metal layer etc. in the resin-made support bodies.

As described above, in the module 10 of the present invention, the bellows-like insulating member 20 is laminated on the bellows-like module main body 11 so as to be uneven, and the through hole 28 of the module main body 11 and the through hole 36 of the insulating member 20 are laminated. And a flexible wire 24 that passes through the module main body 11 and the insulating member 20. That is, the module main body 11 and the insulating member 20 are combined, and both are inserted by the wire 24, thereby maintaining the combined state of the module main body 11 and the insulating member 20 by matching the irregularities of the bellows.
By having such a configuration, the present invention combines the bellows-like module main body 11 with the bellows-like insulating member 20 and the heat radiating member, and the module main body 11 and the insulating member 20 etc. stably. A module 10 is obtained that can maintain the combined configuration, improve handling, and has flexibility, and can be easily attached to, for example, a tubular heat source with good handling. ing.

  As shown in Patent Document 1 and the like, a thermoelectric conversion module having a bellows shape and flexibility is known. In such a flexible bellows-like thermoelectric conversion module, for example, the folded support body can be reduced in the longitudinal direction, that is, thermoelectric conversion, for the purpose of improving the heat transfer efficiency, the mounting density of the thermoelectric conversion elements, etc. It is advantageous to compress the layers in the arrangement direction so that the bellows is closed as much as possible.

However, in the conventional bellows-like thermoelectric conversion module, when the bellows is closed, the electrodes come into contact with each other at the mountain fold portion, causing a short circuit and no power generation.
Therefore, when closing the bellows of the bellows-like thermoelectric conversion module, it is conceivable to combine insulating members.
In the bellows-like thermoelectric conversion module, when some members are combined, it is naturally preferable that the members to be combined are also bellows-like. For example, in an accordion-shaped thermoelectric conversion module, in order to prevent contact between electrodes in a mountain fold, an insulating member obtained by folding a long insulator into a bellows shape is laminated on the thermoelectric conversion module, and the insulating member The structure which covers the connection electrode of a mountain fold part can be considered.
Thereby, even if it is in the state which closed the bellows of the thermoelectric conversion module, it can prevent that the connection electrode of a mountain fold part short-circuits.

Here, if the bellows-like member is simply laminated on the bellows-like thermoelectric conversion module, the bellows-like member is easily detached from the thermoelectric conversion module when the bellows-like member is attached to a heat source or the like. Therefore, for example, when a bellows-like thermoelectric conversion module in which bellows-like members are stacked is attached to a tubular heat source or the like, the bellows-like member and the thermoelectric conversion module are It is necessary to mount the heat source while maintaining the laminated state.
That is, simply stacking a bellows-like member on a bellows-like thermoelectric conversion module results in poor handling and poor workability such as mounting to a heat source. In addition, in order to prevent the bellows-like member from being detached from the thermoelectric conversion module, there is a possibility that the shape of the heat source and the like may be restricted.

On the other hand, the module 10 of the present invention not only laminates the flexible bellows-like module main body 11 and the flexible bellows-like insulating member 20 with the concaves and convexes, but also the module main body 11. The wire 24 penetrates the module main body 11 and the insulating member 20 through the through hole 28 formed in the inclined surface and the through hole 36 formed in the inclined surface of the insulating member 20.
Therefore, even when the module 10 is deformed such as by bending or only one of the module main body 11 and the insulating member 20 is supported, the module main body 11 and the insulating member 20 do not dissociate.

In addition to the module main body 11 and the insulating member 20, the wire 24 is also flexible, and can be bent in the longitudinal direction. For example, it is bent into a curved shape and attached to a tubular heat source. It is possible to attach to various shapes of heat sources. In addition, since the wire 24, that is, the linear member, is inserted through the module main body 11 and the insulating member 20, the bellows can be easily closed by pressing in the longitudinal direction, and the degree of compression by the pressed state, that is, the bellows The interval between the concaves and convexes (the bellows interval) can be easily changed in whole or in part. Moreover, the module main body 11 and the insulating member 20 do not dissociate.
For this reason, it is easy to handle and can be mounted with good workability even when mounted on a heat source having various shapes such as a curved surface and a refracted surface.

  Further, since the module 10 in the illustrated example covers the connection electrode 18 on the mountain fold side and laminates the insulating member 20 with the support 30 facing the module body 11, the bellows of the module 10 is formed as shown in FIG. 1C. Even when closed, the connection electrodes 18 on the mountain fold side can be prevented from coming into contact with each other and short circuiting.

  In the module 10 of the present invention, as the wire 24, various linear members having flexibility can be used. Specifically, metal wires such as threads (strings) and wires, metal wires coated with an insulating material, and the like are exemplified.

In the module 10 of the present invention, the penetration position of the wire 24 in the module main body 11 is preferably other than the portion where the thermoelectric conversion layer and the connection electrode 18 are formed. Thereby, it can prevent that the area of a thermoelectric conversion layer or an electrode reduces, and the intensity | strength of the module 10 is securable. Furthermore, even when the wire 24 having electrical conductivity is used, it is possible to prevent a short circuit from occurring between the thermoelectric conversion layer or electrode and the wire.
In particular, the wire 24 penetrates the inclined surface at the same position as the connection electrode 18 in the longitudinal direction (inclination direction of the inclined surface) in the width direction and in the longitudinal direction (inclination direction of the inclined surface) as in the illustrated example. preferable. When the module 10 is pressed in the longitudinal direction and the bellows is closed (the bellows is folded) as shown in FIG. Therefore, when the bellows is closed by inserting the wire 24 outside the connection electrode 18 in the width direction and at the same position as the connection electrode 18 in the longitudinal direction as in the illustrated example, it is usually formed of a metal material. The connecting electrode can be brought into close contact with the support body 12, and the temperature unevenness of the thermoelectric conversion layer in the width direction and the longitudinal direction can be reduced on the mountain fold side, and efficient power generation can be performed.

As described above, the insulating member 20 is provided with the heat conductive layer 32 made of a metal material or the like on one surface of the insulating support 30 and also functions as a heat radiating member.
Therefore, as conceptually shown in FIG. 3, the height of the mountain fold portion of the insulating member 20 is made higher than the height of the mountain fold portion of the module main body 11, and the mountain fold portion of the insulating member 20 is made to be the module main body 11. You may make it protrude largely from. Thereby, the insulating member 20 is made to act as a radiation fin, the temperature difference of a thermoelectric conversion layer is enlarged, and the electric power generation amount of the module 10 can be enlarged. In the illustrated example, since the wire 24 is inserted in the longitudinal direction at the same position as the connection electrode 18, the connection electrode 18 having high thermal conductivity and the heat conductive layer 32 of the insulating member 20 acting as a heat radiation fin. Can be brought into close contact with each other through the support 30, and the heat dissipation effect can be further improved.

  Further, for example, when the module body 11 side is mounted on a curved surface such as a tubular heat source, the mountain folds of the insulating member 20 are separated from each other, so that the insulating member 20 acts more effectively as a heat radiating fin, The amount can be improved. In this regard, the other aspects are the same.

Here, when the height of the unevenness of the module body 11 is H, and the difference in height between the mountain fold portion (the top portion) of the module body 11 and the mountain fold portion (same as above) of the insulating member 20 is the protrusion amount L. Further, it is preferable that the protruding amount L is 0.5 to 5 times the height H. That is, it is preferable to satisfy “0.5H ≦ L ≦ 5H”.
By setting the protrusion amount L of the mountain fold portion of the insulating member 20 to 0.5 times or more the height H of the unevenness of the module 10, a sufficient heat dissipation effect can be obtained and the power generation amount can be improved.
Further, by making the protrusion amount L of the mountain fold portion of the insulating member 20 not more than 5 times the height H of the unevenness of the module 10, the module 10 can be prevented from becoming unnecessarily large, and the degree of freedom of installation location can be reduced. Improvement, expansion of applications of the module 10 and the like can be achieved.

The height of the mountain folds of the insulating member 20 may be different. That is, the insulating member 20 may have irregularities with different heights (mountain folds with different heights). This configuration is particularly effective when the mountain-folded portion of the insulating member 20 is greatly protruded from the module body 11 as shown in FIG.
At this time, the protrusion amount of the mountain fold portion of the insulating member 20 is set to be the same as the protrusion amount L described above, the protrusion amount at the highest mountain fold portion is the maximum protrusion amount L1, and the protrusion amount of the other mountain fold portions is L2. In this case, the difference Ld between the maximum protrusion amount L1 and the protrusion amount L2 is preferably not less than ½ of the maximum protrusion amount L1. That is, it is preferable that “Ld ≧ 0.5L1 (where Ld = L1−L2)” is satisfied.
In the insulating member 20 having tops with different heights, the difference Ld between the maximum protruding amount L1 and the protruding amount L2 is set to 1/2 or more of the maximum protruding amount L1, so that the protruding portion of the insulating member 20 in the module 10 In addition, it is possible to suitably prevent air from being trapped and improve the heat dissipation effect, thereby obtaining a larger amount of power generation.

FIG. 4A conceptually shows another example of the thermoelectric conversion module of the present invention. FIG. 4B conceptually shows a state in which the bellows of the thermoelectric conversion module shown in FIG. 4A is closed.
In addition, since the thermoelectric conversion module shown to FIG. 4A etc. uses many the same members as the thermoelectric conversion module shown to above-mentioned FIG. 1A etc., the same code | symbol is attached | subjected to the same member and description mainly performs a different site | part. In this regard, other aspects of the thermoelectric conversion module of the present invention are the same, including the thermally conductive laminate of the present invention described later.

The module 10 shown in FIGS. 1A to 1C has a configuration in which an insulating member 20 is laminated on the module main body 11 with the bellows unevenness, and a wire 24 is inserted through both of them.
On the other hand, in the thermoelectric conversion module 40 shown in FIG. 4A, a bellows-like heat radiation member 42 is further laminated on the insulating member 20 of the module 10 with the bellows unevenness, and the insulation member 20 and the heat radiation member 42 A wire 46 as a two-line member is inserted. That is, the heat radiating member 42 is laminated on the surface of the insulating member 20 opposite to the module main body 11. The heat dissipation member 42 is one of the bellows-like members in the present invention.
In the following description, the thermoelectric conversion module 40 is also referred to as “module 40”.

The heat dissipating member 42 is a bellows shape obtained by alternately folding a sheet-like material made of a material having a high thermal conductivity by a mountain fold and a valley fold. In this example, the side that protrudes toward the insulating member 20 of the heat dissipation member 42 is a valley fold, and the opposite side is a mountain fold.
As the material for forming the heat dissipation member 42, various materials exemplified as the material for forming the heat conductive layer 32, such as a metal material, can be used. Further, the folding process for forming the bellows may be performed by a known method such as press working.

In the module 40, the through hole 48 is formed in the vicinity of both end portions in the width direction on the inclined surface of the insulating member 20 formed by the bellows-like folding. In the longitudinal direction, a pair of through holes 48 are formed symmetrically with the folding line of the mountain fold at the mountain fold. The through hole 48 is preferably formed to be linear in the longitudinal direction when the insulating member 20 is folded back in a bellows shape.
On the other hand, the through holes 50 are also formed in the vicinity of both end portions in the width direction on the inclined surface of the heat radiating member 42 formed by the bellows. The through hole 50 is formed at the same position as the through hole 48 in the width direction. Further, a pair of through holes 50 are formed in the longitudinal direction at the valley fold portion symmetrically with respect to the folding line of the valley fold. The through hole 50 is preferably formed to be linear in the longitudinal direction when the heat dissipation member 42 is folded back in a bellows shape. Further, the through hole 50 is preferably formed so that the through hole 48 of the insulating member 20 is also linear when the heat radiating member 42 is laminated on the insulating member 20.

The module 40 is a laminate of the module body 11 and the insulating member 20 through which the wire 24 is inserted, that is, the heat radiating member 42 formed of a heat conductive material is laminated on the insulating member 20 of the module 10 described above, The wire 46 is inserted through the insulating member 20 and the heat radiating member 42 through the through hole 48 of the insulating member 20 and the through hole 50 of the heat radiating member 42.
Therefore, in the module 40, since the heat dissipation member 42 acts as a heat dissipation fin, the temperature difference of the thermoelectric conversion layer can be increased to obtain a large amount of power generation.
Further, the wire 24 is inserted through the module body 11 and the insulating member 20, and the wire 46 is inserted through the insulating member 20 and the heat dissipation member 42. Therefore, as in the module 10 described above, each member does not dissociate, and the bellows can be closed and the irregularities of the bellows can be easily adjusted, that is, the bellows spacing can be easily adjusted. When mounting on a heat source having various shapes such as the above, mounting can be performed with good workability.

In the module 40 having the heat radiating member 42, the protrusion amount of the mountain fold portion of the heat radiating member 42 is the same as the example shown in FIG. 3 described above by replacing the reference of the protrusion amount with the mountain fold portion (the top portion) of the insulating member 20. Is preferable.
In the module 40 having the heat radiating member 42, the heat radiating member 42 may have mountain fold portions having different heights, that is, unevenness having different heights. In this case, it is preferable that the difference in height of the mountain folds of the heat radiating part is the same as in the above-described example.

Further, in the module 40 shown in FIG. 4A and the like, two wires are used, the laminated module main body 11 and the insulating member 20 are inserted by the wire 24, and further, the heat radiating member 42 is laminated to form the insulating member 20 and the heat radiating member. 42 is inserted through a wire 46. However, the thermoelectric conversion module of the present invention is not limited to this.
That is, according to the positional relationship among the module main body 11, the insulating member 20, and the heat radiating member 42, the size of the irregularities of the bellows, the insertion amount of the convex portions into the concave portions between the bellows, the module main body 11 if possible. A common wire may be inserted through the insulating member 20 and the heat dissipation member 42. In this regard, the same applies to a configuration in which three or more bellows-like objects are stacked in various configurations described later. That is, in the present invention, a common wire may be inserted into three or more bellows-like objects in various laminated structures in which three or more bellows-like objects are laminated.

  The thermoelectric conversion module of the present invention has a configuration in which the stacked module main body 11 and the insulating member 20 shown in FIGS. 1A to 1C are inserted by wires 24, and the stacked module main body 11 shown in FIGS. 4A and 4B are insulated. In addition to the structure in which the member 20 is inserted through the wire 24 and the heat dissipating member 42 is stacked and the insulating member 20 and the heat dissipating member 42 are inserted through the wire 46, the bellows-shaped module main body 11 includes Various configurations in which the bellows-like members are laminated can be used.

As an example, as conceptually shown in FIG. 5, the heat dissipation member 42 is provided not on the insulating member 20 but on the lower side of the module main body 11 so as to match the irregularities of the bellows. The structure which penetrated by the wire 52 is illustrated. That is, a configuration in which the heat radiating member 42 is provided not on the insulating member 20 but on the support 12 side of the module main body 11 and the module main body 11 and the heat radiating member 42 are inserted by the wire 52 is exemplified. In other words, the heat radiating member 42 is provided on the support 12 side opposite to the insulating member 20 of the module main body 11, and the module main body 11 is sandwiched between the insulating member 20 on the mountain fold side and the heat radiating member 42 on the valley fold side. A configuration is illustrated.
As another example, as conceptually shown in FIG. 6, the heat dissipating member 42 is combined with the irregularities of the bellows so as to sandwich the configuration in which the module body 11 and the insulating member 20 are laminated and the wire 24 is inserted. A configuration in which the wire 52 is inserted into the heat radiating member 42 and the module main body 11 and the wire 46 is inserted into the insulating member 20 and the heat radiating member 42 can also be used.
Further, in the thermoelectric conversion module shown in FIG. 5, the insulating member 20 is not provided, and the module main body 11 and the heat radiating member 42 are stacked, with the heat radiating member 42 provided on the lower side of the module main body 11, that is, on the support 12 side. Is also available.
The through holes through which the wires (linear members) penetrate are basically the through holes 28 of the module body 11 and the through holes 36 of the insulating member 20, the through holes 48 of the insulating member 20 and the through holes of the heat radiating member 42. Since it is the same, it is omitted in FIGS.

In the above example, the insulating member 20 and the heat radiating member 42 are illustrated as the bellows-like members. However, in the present invention, various members can be used in addition to the bellows-like members. .
Specifically, examples of the bellows-like member other than the insulating member 20 and the heat dissipation member 42 include a member for adjusting the distance between the bellows. As an example, the member for adjusting the distance between the bellows may be formed of metal.

In the thermoelectric conversion module 10 of the present invention, the widths of the insulating member 20 and the heat radiating member 42 are generally equal to the width of the module body 11. However, the present invention is not limited to this.
As an example, as shown in FIG. 7 conceptually illustrating the module 10 shown in FIGS. 1A to 1C, the size of the insulating member 20 in the width direction is made larger than the size of the module body 11 in the width direction. Thus, the insulating member 20 may protrude from the end in the width direction of the module body 11 on one side in the width direction or on both sides in the width direction.
FIG. 7 is a view of the module 10 as viewed in the longitudinal direction, that is, FIG. 1A is a view of the module 10 as viewed from the lateral direction.
Further, as shown in FIGS. 5 and 6, when the heat radiating member 42 is used in addition to the insulating member 20, the insulating member 20 and / or the heat radiating member are similarly formed from the end in the width direction of the module body 11. 42 may protrude. As shown in FIG. 6, when two heat radiating members 42 are provided, one or both heat radiating members 42 may protrude from the end of the module body 11 in the width direction. Further, in the above-described configuration in which the insulating member 20 is not provided and the heat radiating member 42 is provided on the support 12 side of the module main body 11, the heat radiating member 42 protrudes from the end in the width direction of the module main body 11. Also good.

As described above, the insulating member 20 is obtained by forming the heat conductive layer 32 on the surface of the insulating support 30 and can also function as a heat radiating member. Further, the heat radiating member 42 is formed of a material having high thermal conductivity.
Therefore, as shown in FIG. 7, by projecting the insulating member 20 (heat radiating member 42) from the module main body 11 in the width direction, the region projecting from the module main body 11 of the insulating member 20 acts like a radiating fin. Thus, a good heat dissipation effect can be obtained. Therefore, according to this structure, the temperature difference in the thermoelectric conversion layer of the module main body 11 can be enlarged, and the electric power generation amount in a thermoelectric conversion module can be enlarged.

The amount of protrusion in the width direction of the insulating member 20 from the module body 11 may be set as appropriate according to the size of the module 10, the assumed installation location of the module 10, and the like.
Specifically, as shown in FIG. 7, when the width of the module main body 11 is W and the protrusion amount of the insulating member 20 (heat radiation member 42) in the width direction from the module main body 11 is P, the protrusion amount P However, it is preferably 0.1 to 10 times the width W of the module main body 11. That is, it is preferable to satisfy “0.1 W ≦ P ≦ 10 W”.
By setting the protrusion amount P of the insulating member 20 in the width direction to be 0.1 times or more the width W of the module main body 11, a sufficient heat dissipation effect can be obtained and the power generation amount can be improved.
Further, by making the protruding amount P of the insulating member 20 in the width direction 10 times or less the width W of the module body 11, the module 10 is prevented from becoming unnecessarily large, and the degree of freedom in installation location is improved. The use of the module 10 can be expanded.

In the configuration in which the heat radiating member 42 protrudes from the module body 11 in the width direction, the heat radiating member 42 may protrude from the insulating member 20 as shown in FIG. 4A, but there is almost no protruding amount from the insulating member 20. Also good.
That is, when the heat radiating member 42 is protruded in the width direction from the module body 11, the difference between the height of the mountain fold portion of the heat radiating fin and the height of the mountain fold portion of the insulating member 20 is equal to the thickness of the heat radiating member 42. It may be only.
The same applies to the thermoelectric conversion modules shown in FIGS. 5 and 6.

The above example is an example in which the bellows-like module main body 11 is combined with the bellows-like insulating member 20 and / or the bellows-like heat dissipation member 42 as the bellows-like member. A bellows-like thermoelectric conversion member can also be used.
An example is shown in FIG.

The thermoelectric conversion module 70 shown in FIG. 8 has two bellows-shaped thermoelectric conversion members 72 laminated on the support body 12 side of the module main body 11 so as to match the irregularities, and the module main body 11 and the two thermoelectric conversion members 72 are stacked. The wire 74 is inserted. In addition, in the thermoelectric conversion module 70 shown in FIG. 8, the module main body 11 does not have the through-hole 28 and the reinforcement member 28a which are formed in a mountain fold part.
In the following description, the thermoelectric conversion module 70 is also referred to as “module 70”.

The thermoelectric conversion member 72 has thermoelectric conversion layers that are formed on one surface of the support and are separated from each other, and connection electrodes that connect adjacent thermoelectric conversion layers. The thermoelectric conversion member 72 also performs power generation by thermoelectric conversion, like the module body 11. That is, the module main body 11 and the thermoelectric conversion member 72 are both accordion-shaped power generation modules that generate power by thermoelectric conversion.
The thermoelectric conversion member 72 shown by FIG. 8 has the structure similar to the module main body 11 as a preferable aspect.
That is, the thermoelectric conversion member 72 has alternately the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n having a certain length at regular intervals in the longitudinal direction of the long support 12. In addition, the thermoelectric conversion member 72 has a connection electrode 18 that connects the adjacent P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n. It has a bellows-like shape folded back.

One of the two thermoelectric conversion members 72 is laminated on the module main body 11 with the support 12 of the module main body 11 facing its own thermoelectric conversion layer (member thermoelectric conversion layer).
The other thermoelectric conversion member 72 is laminated on the thermoelectric conversion member 72 so that the support 12 (member support) of the thermoelectric conversion member 72 laminated on the module main body 11 faces its thermoelectric conversion layer. .

On the inclined surface of the module body 11, through holes 76 are formed in the valley fold portions in the vicinity of both end portions in the width direction. Preferably, the through hole 76 is formed in a reinforcing member similar to the reinforcing member 28a.
Similar to the through-hole 28, as a preferred embodiment, the through-hole 76 is preferably formed in the width direction in the region where the connection electrode 18 and the P-type thermoelectric conversion layer 14 p and the N-type thermoelectric conversion layer 16 n in the width direction of the support 12 are formed. Located outside. In addition, the through hole 28 is symmetrical with respect to the center of the connection electrode 18 in the longitudinal direction (refer to the folded line shown by a one-dot chain line in FIG. 2) at the same position as the connection electrode 18 that is valley-folded in the longitudinal direction. A pair is formed at the position.
Further, like the through hole 28, the through hole 76 is preferably formed at a position that is linear in the longitudinal direction when the support 12 is folded back in a bellows shape.

Also in the thermoelectric conversion member 72, through holes 78 are formed in the valley folds in the vicinity of both end portions in the width direction of the inclined surface. Preferably, the through hole 78 is also formed in the same reinforcing member as the reinforcing member 28a.
Specifically, the through hole 78 of the thermoelectric conversion member 72 is formed at the same position as the through hole 76 of the module body 11 in the width direction. Further, in the longitudinal direction, a pair is formed at the valley fold portion at positions symmetrical to the folding line of the valley fold.
The through-hole 78 is preferably formed at a position that is linear in the longitudinal direction when the thermoelectric conversion member 72 is folded back in a bellows shape. Further, the through-hole 78 is preferably formed so as to be linear with the through-hole 76 of the module body 11 when the thermoelectric conversion member 72 is laminated on the module body 11.

In the module 70, the module main body 11 and the two thermoelectric conversion members 72 are inserted by wires 74 through the through holes 76 of the module main body 11 and the through holes 78 of the thermoelectric conversion member 72.
Therefore, in the module 70, as in the module 10 described above, each member does not dissociate, and the bellows can be closed and the interval between the bellows unevenness, that is, the interval between the bellows can be easily adjusted, so that the handling is good. Therefore, when mounting on a heat source having various shapes such as a curved surface, the mounting can be performed with good workability. In addition, the module 70 has a configuration in which three accordion-shaped power generation modules that generate power substantially by thermoelectric conversion are stacked, so that a large amount of power generation can be obtained. Furthermore, since the thermoelectric conversion layer of the module main body 11 and the thermoelectric conversion member 72 is laminated facing the support 12 of another member, it is possible to prevent a short circuit of the thermoelectric conversion layer when the bellows is closed.

As described above, similarly to the module body 11, the thermoelectric conversion member 72 is a single bellows-shaped power generation module that generates power by thermoelectric conversion. Moreover, in the example of illustration, as a preferable aspect, the thermoelectric conversion member 72 has the same structure as the module main body 11.
In the present invention, in such a configuration having a plurality of accordion-shaped power generation modules that perform power generation by thermoelectric conversion, any accordion-shaped power generation module can be regarded as a module body in the thermoelectric conversion module of the present invention. Good.
Therefore, in the module 70, any one of the bellows-shaped power generation modules of the thermoelectric conversion member 72 and the module main body 11 may be regarded as the module main body in the present invention.

For example, in the above description, the module 70 shown in FIG. 8 includes the module body 11 and the thermoelectric conversion member 72 laminated on the support 12 of the module body 11 with the thermoelectric conversion layer (member thermoelectric conversion layer) facing each other. The thermoelectric conversion member 72 is laminated on the support 12 (member support) of the thermoelectric conversion member 72 so as to face the thermoelectric conversion layer (module main body 11 / thermoelectric conversion member 72 / thermoelectric conversion). Configuration of member 72).
However, the module 70 shown in FIG. 8 is supported by the module main body 11, the thermoelectric conversion member 72 laminated on the support body 12 of the module main body 11 so as to face the thermoelectric conversion layer, and the thermoelectric conversion layer of the module main body 11. It can also be regarded as a configuration having a thermoelectric conversion member 72 laminated facing the body 12 (configuration of thermoelectric conversion member 72 / module body 11 / thermoelectric conversion member 72).
Alternatively, the module 70 includes a module main body 11, a thermoelectric conversion member 72 laminated on the thermoelectric conversion layer of the module main body 11 so as to face the support 12, and a thermoelectric conversion layer on the support 12 of the thermoelectric conversion member 72. Can be regarded as a configuration having a thermoelectric conversion member 72 laminated facing each other (thermoelectric conversion member 72 / thermoelectric conversion member 72 / module main body 11 configuration).

In this regard, the same applies to the case where a plurality of bellows-like power generation modules are provided and the configuration of the bellows-like power generation modules is different as will be described later. A single module may be regarded as a module body in the present invention.
For example, when the thermoelectric conversion module of the present invention has a single bellows-shaped power generation module having the same configuration as the module main body 84 shown in FIG. 10 described later and a single bellows-shaped power generation module having the same configuration as the module main body 11. The module main body 84 may have the same configuration as the module main body in the present invention, and the module main body 11 may have the same configuration as the thermoelectric conversion member in the present invention. May be regarded as the module body in the present invention, and the same structure as the module body 84 may be regarded as the thermoelectric conversion member in the present invention.

The module 70 shown in FIG. 8 has two thermoelectric conversion members 72, but the present invention is not limited to this. That is, the thermoelectric conversion module of the present invention may have a configuration in which two accordion-shaped power generation modules each having only one thermoelectric conversion member 72 are stacked. In this case, the thermoelectric conversion member 72 may be stacked on the thermoelectric conversion layer side of the module body 11 or may be stacked on the support 12 side.
Or the structure which laminated | stacked the 4 or more bellows-shaped electric power generation module single-piece | unit which has the thermoelectric conversion member 72 3 or more may be sufficient.

In the module 70 shown in FIG. 8, the module main body 11 and the thermoelectric conversion member 72 have the same configuration. However, the present invention is not limited to this.
That is, in the present invention, in the configuration having the thermoelectric conversion member as the bellows-like member, the shape and / or position of the thermoelectric conversion layer, the shape and / or position of the connection electrode, and the thermoelectric conversion layer of the module body and the thermoelectric conversion member The types (both P-type and N-type, only P-type, only N-type) and the like may be different (see FIGS. 10 and 11 described later). That is, the configuration may be different between the module body and the thermoelectric conversion member. Moreover, when it has a some thermoelectric conversion member, a structure may differ between thermoelectric conversion members.
In this case, as described above, any bellows-shaped power generation module alone may be regarded as the module body in the present invention.
However, as shown in a second aspect of the manufacturing method of the present invention, which will be described later, a plurality of bellows-like shapes are possible in that the bellows-like shape can be folded back in a state where the module main body 11 and the thermoelectric conversion member 72 are laminated. In this case, it is preferable that the positions of the mountain fold and the valley fold are the same for all the bellows-shaped power generation modules, and as shown in FIG. The same configuration is particularly preferred.

The thermoelectric conversion module of the present invention may have the insulating member 20 and / or the heat radiating member 42 even in such a configuration having one or more bellows-like thermoelectric conversion members.
For example, like the thermoelectric conversion module 80 shown in FIG. 9, the module 70 shown in FIG. 8 may be provided with the insulating member 20 similarly to the module 10 shown in FIGS. 1A to 1C.
Alternatively, in the module 40 shown in FIG. 4, the thermoelectric conversion module shown in FIG. 5, the thermoelectric conversion module shown in FIG. 6, or the like, the module main body 11 has one or more thermoelectric conversion members 72 (corrugated shape that generates power by thermoelectric conversion). May be laminated.
Further, in the module 10 shown in FIGS. 1A to 1C, a thermoelectric conversion member 72 may be provided on the insulating member 20.

Further, in the example shown in FIG. 8, the module body 11, the thermoelectric conversion member 72, and the thermoelectric conversion members 72 are laminated with the support 12 and the thermoelectric conversion layer facing each other. This is not limited.
For example, as shown in FIG. 8, when the module main body 11 and the thermoelectric conversion member 72 have the same configuration, the thermoelectric conversion member 72 is turned upside down, the thermoelectric conversion layers face each other, and the module main body 11 and The thermoelectric conversion member 72 may be laminated. In other words, as shown in FIG. 8, when the module body 11 and the thermoelectric conversion member 72 have the same configuration, the mountain fold and the valley fold in the alternate long and short dash line (see FIG. 2) are reversed. The module body 11 and the thermoelectric conversion member 72 may be laminated with the thermoelectric conversion layers facing each other.
In this case, the P-type thermoelectric conversion layers 14p are in contact with each other and the N-type thermoelectric conversion layers 16n are in contact with each other in the module body 11 and the thermoelectric conversion member 72. Therefore, even if the module body 11 and the thermoelectric conversion member 72 are laminated with the thermoelectric conversion layer facing each other, no short circuit occurs.

In the above example, the module main body 11 is provided with the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n alternately on the inclined surface on one surface of the support 12 folded in a bellows shape and adjacent to each other. Although the P-type thermoelectric conversion layer 14p and the N-type thermoelectric conversion layer 16n are connected by the connection electrode 18 straddling adjacent inclined surfaces, the present invention is not limited to this, and various configurations can be used. is there.
For example, the module main body (thermoelectric conversion member) may be provided with a P-type thermoelectric conversion layer 14p and an N-type thermoelectric conversion layer 16n on one inclined surface of the support body 12 folded in a bellows shape so as to be separated from each other. .

An example is shown in FIG.
The module main body 84 shown in FIG. 10 uses many of the same members as those of the module main body 11 shown in FIG. To do. The same applies to the module main body 95 shown in FIG.
Moreover, these module main bodies can be used also as a thermoelectric conversion member.

FIG. 10 is a conceptual diagram in which the module main body 84 is extended in a planar shape as in FIG. In FIG. 10, the mountain folds and the valley folds of the support 12 are alternately performed by a one-dot chain line. That is, the space between the alternate long and short dash lines is an inclined surface of the support 12 that is folded back in a bellows shape.
10 includes an inclined surface having a P-type thermoelectric conversion layer 86p, an N-type thermoelectric conversion layer 90n, and a P-type thermoelectric conversion layer 86p that are separated from each other, and an N-type thermoelectric conversion layer 90n and a P-type that are separated from each other. The inclined surfaces having the thermoelectric conversion layers 86p and the N-type thermoelectric conversion layers 90n are alternately provided in the longitudinal direction.

In the inclined surface having the P-type thermoelectric conversion layer 86p, the N-type thermoelectric conversion layer 90n, and the P-type thermoelectric conversion layer 86p, the two P-type thermoelectric conversion layers 86p sandwich the N-type thermoelectric conversion layer 90n in the width direction. A thermoelectric conversion layer is disposed.
On this inclined surface, the P-type thermoelectric conversion layer 86p, the N-type thermoelectric conversion layer 90n, and the P-type thermoelectric conversion layer 86p are connected in series by two connection electrodes 94. The connection electrode 94 connects one P-type thermoelectric conversion layer 86p and the N-type thermoelectric conversion layer 90n so as to sandwich the N-type thermoelectric conversion layer 90n in the longitudinal direction, and the N-type thermoelectric conversion layer 90n and the other P-type thermoelectric conversion layer 90n. The conversion layer 86p is connected.
On the other hand, on the inclined surface having the N-type thermoelectric conversion layer 90n, the P-type thermoelectric conversion layer 86p, and the N-type thermoelectric conversion layer 90n, the two N-type thermoelectric conversion layers 90n sandwich the P-type thermoelectric conversion layer 86p in the width direction. In addition, a thermoelectric conversion layer is disposed.
On this inclined surface, the N-type thermoelectric conversion layer 90n, the P-type thermoelectric conversion layer 86p, and the N-type thermoelectric conversion layer 90n are connected in series by two connection electrodes 94. The connection electrode 94 connects one N-type thermoelectric conversion layer 90n and the P-type thermoelectric conversion layer 86p so as to sandwich the P-type thermoelectric conversion layer 86p in the longitudinal direction, and the P-type thermoelectric conversion layer 86p and the other N-type thermoelectric conversion layer 86p. The conversion layer 90n is connected.

In the adjacent inclined surface, at one end in the width direction, the N-type thermoelectric conversion layer 90n and the P-type thermoelectric conversion layer 86p are connected by the connection electrode 92 straddling the ridge line of the inclined surface. The connection between the N-type thermoelectric conversion layer 90n and the P-type thermoelectric conversion layer 86p on the adjacent inclined surfaces by the connection electrode 92 is alternately performed in the thermoelectric conversion layer at the end in the width direction.
Thereby, all the P-type thermoelectric conversion layers 86p and N-type thermoelectric conversion layers 90n formed on the support 12 are alternately connected in series.

In the above example, as a preferred embodiment, the module body has both an N-type thermoelectric conversion layer and a P-type thermoelectric conversion layer, but the present invention is not limited to this, and the module body (thermoelectric conversion member) A configuration having only an N-type thermoelectric conversion layer or a P-type thermoelectric conversion layer may be used.
An example is shown in FIG.

FIG. 11 is also a conceptual diagram in which the module main body is extended in a planar shape, similarly to FIG. Also in FIG. 11, the mountain fold and the valley fold of the support 12 are alternately performed by a one-dot chain line.
A module main body 95 shown in FIG. 11 includes an inclined surface having two P-type thermoelectric conversion layers 86p in the vicinity of the end in the width direction, and an inclined surface having one P-type thermoelectric conversion layer 86p in the center in the width direction. Alternating in the longitudinal direction.

On the inclined surface having the two P-type thermoelectric conversion layers 86p in the vicinity of the end in the width direction, the two P-type thermoelectric conversion layers 86p are connected by the connection electrode 96. The connection of the P-type thermoelectric conversion layer 86p by the connection electrode 96 is performed at the ends of the two P-type thermoelectric conversion layers 86p on the opposite side in the longitudinal direction.
In this inclined surface, the connection electrode 92 straddling the ridgeline of the inclined surface is connected to the two P-type thermoelectric conversion layers 86p. The connection electrodes 92 connected to each P-type thermoelectric conversion layer 86p reach different inclined surfaces.

On the inclined surface having one P-type thermoelectric conversion layer 86p at the center in the width direction, two connection electrodes 98 are connected to the P-type thermoelectric conversion layer 86p with the P-type thermoelectric conversion layer 86p sandwiched in the longitudinal direction.
One connection electrode 98 is connected to a connection electrode 92 that straddles one ridge line on the inclined surface side. The other connection electrode 98 is connected to a connection electrode 92 that straddles the ridge line on the inclined surface side opposite to the longitudinal direction.
Thereby, many P-type thermoelectric conversion layers 86p formed in the support body 12 are connected in series.

In the above example, the module body has the thermoelectric conversion layer only on one surface of the support, but the present invention is not limited to this. That is, in the thermoelectric conversion module of the present invention, the module body (thermoelectric conversion member) may have thermoelectric conversion layers on both sides of the support.
Furthermore, in the thermoelectric conversion module of the present invention, the thermoelectric conversion member has a thermoelectric conversion member and the thermoelectric conversion layer of the module body and the thermoelectric conversion layer of the thermoelectric conversion member face each other, or the thermoelectric conversion between the thermoelectric conversion members When laminating the layers facing each other, a bellows-like insulating member made of only an insulating material may be provided between the module body and the thermoelectric conversion layer, or the thermoelectric power of the module body and / or the thermoelectric conversion layer may be provided. The conversion layer may be covered with an insulating film.

In FIG. 12, an example of the heat conductive laminated body of this invention is shown notionally.
A heat conductive laminate 56 shown in FIG. 12 is formed by laminating the insulating member 20 and the heat radiating member 42 together with the bellows of the bellows, and penetrates the through hole of the insulating member 20 and the through hole 50 of the heat radiating member. Then, the insulating member 20 and the heat radiating member 42 are inserted through the wire 46.
That is, the heat conductive laminate 56 is obtained by removing the module main body 11 from the module 10 shown in FIG. 4A. In other words, the module 10 shown in FIG. 4A is a combination of the module main body 11 and the heat conductive laminate 56 shown in FIG.

As described above, the insulating member 20 is obtained by forming the heat conductive layer 32 on one surface of the support 30 as a preferred embodiment.
However, like the module 10 described above, the thermally conductive laminate 56 of the present invention is not limited to this, and the insulating member 20 is formed by folding an insulating sheet-like material such as a resin film into a bellows shape. Only the structure may be sufficient.

  Hereinafter, with reference to the conceptual diagrams of FIGS. 13 to 16B, the first aspect of the method for manufacturing the module 10 shown in FIG. A method for producing a conductive laminate will be described.

  First, as shown in FIG. 13, a long bellows-like module body 11 in which a wire 24 is inserted through a through hole 28 formed in an inclined surface by bellows folding, and an inclined surface by bellows folding. A long bellows-like insulating member 20 in which the wire 60 is inserted through the through hole 36 is produced.

Next, as shown in FIG. 14, the module main body 11 through which the wire 24 is inserted and the insulating member 20 through which the wire 60 is inserted are conveyed in the longitudinal direction, and the conveyance path of the module main body 11 is bent by 90 ° by a roller 62. Similarly, the conveyance path of the insulating member 20 is bent 90 ° by the roller 64.
The module body 11 and the insulating member 20 are transported at the time when the transport path is bent by the rollers 62 and 64, the thermoelectric conversion layer forming surface of the module body 11, the support 30 of the insulating member 20, and the like. Do so as to face each other.
As shown in FIGS. 14 and 15A, the module main body 11 and the insulating member 20 are laminated together with the bellows unevenness at a place where the module main body 11 and the insulating member 20 are bent by 90 °, that is, a place where the conveyance path is changed. .

In the present invention, at least one of the transport paths is changed while transporting the long bellows-like module body 11 and the insulating member 20 in the longitudinal direction, and the module body 11 and the insulating member 20 are changed at the change point of the transport path. Can be easily laminated by aligning the irregularities of the module main body 11 and the insulating member 20.
Moreover, since the module main body 11 is conveyed in the state where the wire 24 and the insulating member 20 are respectively inserted through the wire 60, even if conveyance in the longitudinal direction, change of the conveyance path and lamination are performed, an appropriate bellows The shape can be maintained. Therefore, it is possible to stably stack the proper module body 11 and the insulating member 20 with the unevenness.

In the illustrated example, the transfer path of the module main body 11 and the insulating member 20 is changed by the cylindrical rollers 62 and 64, but the present invention is not limited to this. For example, the conveyance path of the module main body 11 and the insulating member 20 conveyed in the longitudinal direction is changed by using a roller or gear having irregularities according to the bellows of the module main body 11 or irregularities according to the bellows of the insulating member 20. May be.
Further, only one of the module main body 11 and the insulating member 20 may be changed in order to change the transport path in order to stack the module main body 11 and the insulating member 20 with the unevenness.

As shown in FIGS. 14 and 15A, when the module main body 11 and the insulating member 20 are laminated by aligning the unevenness, as shown in FIG. 15B, the wire 24 from the module main body 11 and the wire 60 from the insulating member 20 are respectively connected. Pull out.
Next, as shown in FIG. 16A, the module body 11 and the insulating member 20 are aligned. In this example, the module main body 11 and the insulating member 20 are aligned so that the through holes 28 of the module main body 11 and the through holes of the insulating member 20 are linearly arranged.
Further, as shown in FIG. 16B, the wire 24 pulled out from the module body 11 is inserted so as to penetrate the through hole 28 of the module body 11 and the through hole of the insulating member 20. Thereby, the long bellows-like module main body 11 and the insulating member 20 are combined with the irregularities of the bellows, and the module 10 of the present invention is inserted through the wire 24.
Therefore, in this example, the wire 24 pulled out from the module main body 11 becomes a fixing linear member. Of course, the wire 60 drawn from the insulating member 20 may be used as the fixing linear member.

In the example shown in FIGS. 13 to 16B, after the module main body 11 and the insulating member 20 are laminated, the wire 24 and the wire 60 are pulled out and aligned, and then the wire 24 is inserted again.
On the other hand, in another form of the first aspect of the manufacturing method of the thermoelectric conversion module of the present invention, the module body 11 and the insulating member 20 are connected with another wire without pulling out the wire 24 and the wire 60. Insert.

That is, in this method, as shown in FIG. 15A, in a state where the module main body 11 and the insulating member 20 are laminated, alignment is performed as necessary, and the wire 24 and the wire 60 are not pulled out and left as they are. The module main body 11 and the insulating member 20 are inserted through a wire that is a fixing linear member different from the wire 60.
At this time, a through-hole through which a wire serving as a fixing linear member passes is formed in advance at predetermined positions on the inclined surfaces of the module body 11 and the insulating member 20. Or you may form a through-hole by penetrating the wire used as the linear member for fixation to the inclined surface of the module main body 11 and the insulating member 20. FIG.

Although the above description is a manufacturing method of the module shown in FIG. 1A, the thermoelectric conversion module shown in FIGS. It can be manufactured by repeating.
Also, the heat conductive laminate 56 shown in FIG. 12 can be similarly manufactured using the bellows-like insulating member 20 through which the linear member is inserted and the bellows-shaped heat dissipation member 42 through which the linear member is inserted.
In addition, the module 40 shown in FIG. 4A may be manufactured in the same manner using the heat conductive laminate 56 shown in FIG. 12 and the module main body 11 inserted with the wire 24 shown in FIG. In this case, a wire may be inserted separately at a position corresponding to the through hole 36 of the insulating member 20.
Furthermore, in the manufacturing method of the present invention, a thermoelectric conversion module in which the module main bodies 11 are laminated can be manufactured by regarding one or more module main bodies different from the module main bodies 11 as bellows-like members.

In FIG. 17A-FIG. 17C, an example of the 2nd aspect of the manufacturing method of the thermoelectric conversion module of this invention is shown notionally.
The manufacturing method illustrated in FIGS. 17A to 17C is a manufacturing method for manufacturing the module 70 illustrated in FIG. 8 as an example. That is, the second aspect of the manufacturing method of the present invention is a method suitable for manufacturing a thermoelectric conversion module having a configuration in which a plurality of accordion-shaped power generation modules having the same configuration are stacked as shown in FIG. is there.

First, as shown to FIG. 17A, the laminated body which laminated | stacked the module main body 11 before bending in a bellows shape and the thermoelectric conversion member 72 before bending in a bellows shape is produced.
17A to 17C show a method for manufacturing the module 70 shown in FIG. Therefore, in addition to the module main body 11, the thermoelectric conversion member 72 has two sheets, and the second flat plate thermoelectric conversion member 72 is laminated on the first flat plate thermoelectric conversion member 72. The flat module main body 11 is laminated on the second flat thermoelectric conversion member 72.

Next, as shown in FIG. 17B, the laminate is bent into a bellows shape.
As a method of folding the laminated body into a bellows shape, various known methods for folding a sheet-like material or a laminated body of sheet-like materials into a bellows shape, such as a method of inserting between gears that mesh with each other, can be used. .

Finally, as shown in FIG. 17C, the thermoelectric conversion member 72, the thermoelectric conversion member 72, and the inclined surface of the module main body 11 bent in a bellows shape are penetrated to the thermoelectric conversion member 72, the thermoelectric conversion member 72, and the module main body 11. By inserting the wire 74, a module 70 as shown in FIG. 8 is obtained.
Note that the through hole 76 of the module main body 11 that penetrates the wire 74 and the through hole 78 of the thermoelectric conversion member 72 may be formed in a state before being bent into the bellows shape shown in FIG. 17A, and the laminate shown in FIG. 17B. May be formed at the stage of bending the bellows into a bellows shape. Alternatively, the through hole 76 and the through hole 78 may be formed by inserting the wire 74 after being bent into a bellows shape.

  Further, after the module 70 is manufactured in this way, the insulating member as shown in FIG. 9 is obtained by implementing the first aspect of the manufacturing method of the present invention as shown in FIGS. 13 to 16B described above. A module 80 having 20 or the like can also be manufactured.

  As described above, the thermoelectric conversion module and the heat conductive laminate of the present invention, and the method of manufacturing the thermoelectric conversion module and the method of manufacturing the heat conductive laminate have been described, but the present invention is not limited to the above-described examples, Of course, various improvements and modifications may be made without departing from the scope of the present invention.

  It can be suitably used for power generation devices and their manufacture.

10, 40, 70, 80 (Thermoelectric conversion) module 11, 84, 95 Module body 12, 30 Support body 14p, 86p P-type thermoelectric conversion layer 16n, 90n N-type thermoelectric conversion layer 18, 92, 94, 96, 98 Connection Electrode 20 Insulating member 24, 46, 52, 60, 74 Wire 28, 36, 48, 50, 76, 78 Through hole 32 Thermally conductive layer 42 Heat radiating member 62, 64 Roller

Claims (29)

A module main body having a support folded back in a bellows shape, a plurality of thermoelectric conversion layers spaced apart from each other, and a connection electrode connecting adjacent thermoelectric conversion layers formed on at least one surface of the support ,
One or more bellows-like members folded in a bellows shape provided in combination with the module main body and the unevenness; and
The module main body and at least one of the bellows-shaped members can be inserted through the inclined surface of the module main body by the bellows-like folding and the inclined surface of the at least one bellows-like member by folding the bellows. A thermoelectric conversion module comprising a flexible linear member.   The thermoelectric conversion module according to claim 1, wherein the bellows-like member is one or more selected from an insulating member, a heat dissipation member, and a thermoelectric conversion member.   The thermoelectric conversion module according to claim 2, wherein the insulating member is provided so as to face a formation surface of the thermoelectric conversion layer of the module body.   The thermoelectric conversion module according to claim 3, wherein the heat dissipating member is provided facing a surface of the insulating member opposite to the module main body.   The thermoelectric conversion module according to claim 4, further comprising a flexible second linear member that passes through the inclined surface of the insulating member and the inclined surface of the heat radiating member and passes through the insulating member and the heat radiating member. .   The said insulating member has a heat conductive layer on the surface of an insulating layer, The said insulating layer is provided toward the formation surface of the thermoelectric conversion layer of the said module main body in any one of Claims 2-5. The thermoelectric conversion module as described.   The thermoelectric conversion member is connected to a member support folded back in a bellows shape, a plurality of member thermoelectric conversion layers formed on at least one surface of the member support, and the adjacent thermoelectric conversion layers The thermoelectric conversion module of any one of Claims 2-6 which has a member connection electrode to perform. The module main body has the thermoelectric conversion layer only on one side of the support, and the thermoelectric conversion member has the member thermoelectric conversion layer only on one side of the member support. Yes,
The thermoelectric conversion member provided on the thermoelectric conversion layer of the module main body facing the member support, and the thermoelectric conversion member provided on the support of the module main body facing the member thermoelectric conversion layer are few. The thermoelectric conversion module according to claim 7 which has one side. A plurality of the thermoelectric conversion members,
The thermoelectric conversion module according to claim 8, wherein the thermoelectric conversion module has one or more combinations of thermoelectric conversion members provided to face the member support and the member thermoelectric conversion layer.   The thermoelectric conversion module according to any one of claims 1 to 9, wherein the linear member penetrates a place other than the formation position of the thermoelectric conversion layer and the formation position of the connection electrode in the module body. 11. The thermoelectric conversion module according to claim 10, wherein the linear member penetrates the outside in the longitudinal direction of the ridge line formed by the bellows-like folding at the same position in the inclined direction of the inclined surface with respect to the connection electrode. .

  The thermoelectric conversion layer of the module main body is a P-type thermoelectric conversion layer and an N-type thermoelectric conversion layer that are alternately provided on the inclined surface on one side of the support, respectively. The thermoelectric conversion module according to item. An insulating member folded in a bellows shape,
The heat dissipating member folded in the shape of a bellows, provided to match the insulating member and the unevenness, and
A flexible linear member that passes through the inclined surface of the insulating member due to the bellows-like folding and the inclined surface due to the bellows-like folding of the heat radiating member, and passes through the insulating member and the heat radiating member; A thermally conductive laminate characterized by comprising.   The thermally conductive laminate according to claim 13, wherein the insulating member has a thermally conductive layer on the surface of the insulating layer. A support folded back in an accordion shape, a plurality of thermoelectric conversion layers spaced apart from each other, formed on at least one surface of the support, a connection electrode connecting the adjacent thermoelectric conversion layers, and the accordion-like shape A step of producing a module body having a flexible linear member that penetrates the bellows through the inclined surface by folding,
A step of producing a bellows-like member having a flexible linear member that is folded into a bellows shape and passes through the inclined surface by the bellows-like folding;
The step of laminating the module main body and the bellows-like member together with the concavities and convexities in the transport path changing portion provided in the transport path while transporting the module main body and the bellows-like member in a direction perpendicular to the ridge line due to the bellows-like folding.
Providing a flexible fixing linear member that passes through the inclined surface of the module main body and the inclined surface of the bellows-like member and passes through the stacked module main body and the bellows-like member. A method of manufacturing a thermoelectric conversion module characterized by The fixing linear member is at least one of a linear member that passes through the module main body and a linear member that passes through the bellows-like member;
In the step of inserting the fixing linear member, the step of pulling out the linear member from the laminated module main body and the bellows-like member, the step of aligning the module main body and the bellows-like member, and the linear shape The thermoelectric conversion module according to claim 15, wherein a step of inserting at least one of a linear member extracted from the module main body and a linear member extracted from the bellows-like member is inserted into a through-hole of the slope from which the member is extracted. Production method.   In the step of inserting the fixing linear member, the linear member for inserting the module main body and the linear member for inserting the bellows-like member are left as they are, and the fixing linear member is attached to the module main body and the bellows-like member. The method for manufacturing a thermoelectric conversion module according to claim 15, wherein the member is inserted.   The method of manufacturing a thermoelectric conversion module according to any one of claims 15 to 17, wherein the bellows-like member is one or more selected from an insulating member, a heat dissipation member, and a thermoelectric conversion member.   The insulating member and the heat dissipating member are laminated with unevenness, and the insulating member and the heat dissipating member are inserted through the inclined surface of the insulating member and the inclined surface of the heat dissipating member. The manufacturing method of the thermoelectric conversion module of Claim 18 which provides a linear member.   The method for manufacturing a thermoelectric conversion module according to claim 18 or 19, wherein the insulating member has a heat conductive layer on a surface of the insulating layer.   The thermoelectric conversion member is connected to a member support body folded in a bellows shape, a plurality of member thermoelectric conversion layers formed on at least one surface of the support body, and the adjacent member thermoelectric conversion layers. The manufacturing method of the thermoelectric conversion module of any one of Claims 18-20 which has a member connection electrode to perform.   The thermoelectric conversion module according to any one of claims 15 to 21, wherein the fixing linear member is passed through a place other than a formation position of the thermoelectric conversion layer of the module body and a formation position of the connection electrode. Manufacturing method.   23. The method of manufacturing a thermoelectric conversion module according to claim 22, wherein the fixing linear member is penetrated through the outside in the longitudinal direction of the ridge line at the same position in the inclination direction of the inclined surface with respect to the connection electrode. .   The thermoelectric conversion layer of the module body is a P-type thermoelectric conversion layer and an N-type thermoelectric conversion layer that are alternately provided on the inclined surface on one side of the support. The manufacturing method of the thermoelectric conversion module of description. Laminating a plurality of sheet-like materials each having a support, a plurality of thermoelectric conversion layers that are formed on at least one surface of the support and spaced apart from each other, and a connection electrode that connects the adjacent thermoelectric conversion layers The process of
A step of folding the sheet-like laminate into a bellows shape ;
A step of inserting a flexible linear member through the inclined surface of the sheet-like material folded back in the bellows shape by the bellows-like folding ,
A step of laminating at least one of the insulating member and the heat dissipating member folded in a bellows shape on the sheet material folded in a bellows shape together with the irregularities of the bellows; and
The laminated sheet-like material folded in a bellows shape and at least one of the insulating member and the heat radiating member folded in a bellows shape are penetrated through an inclined surface by the bellows-like folding, and a flexible wire A method for manufacturing a thermoelectric conversion module, comprising a step of inserting a shaped member . A step of producing an insulating member having a flexible linear member that is folded into a bellows shape and penetrates the inclined surface by the bellows-like folding;
A step of producing a heat dissipating member having a flexible linear member that is folded into a bellows shape and penetrates the inclined surface by the bellows-like folding;
While transporting the insulating member and the heat dissipation member in a direction orthogonal to the ridge line by the bellows-like folding, the insulating member and the heat dissipation member are laminated with the unevenness in the changing portion of the transport path provided in the transport path. And the process of
And a step of inserting a flexible fixing linear member through the inclined surfaces of the laminated insulating member and heat radiating member. The fixing linear member is at least one of a linear member that passes through the inclined surface of the insulating member and a linear member that passes through the inclined surface of the heat dissipation member;
In the step of inserting the linear member for fixing, the step of pulling out the linear member from the laminated insulating member and the heat radiating member, the step of aligning the insulating member and the heat radiating member, and the linear member 27. The manufacturing of the thermally conductive laminate according to claim 26, wherein the step of inserting at least one of a linear member extracted from the insulating member and a linear member extracted from the heat radiating member into the through-hole of the extracted slope is performed. Method.   In the step of inserting the fixing linear member, the linear member for inserting the insulating member and the linear member for inserting the heat dissipating member are left as they are, and the fixing linear member is attached to the insulating member and the heat dissipating member. The manufacturing method of the heat conductive laminated body of Claim 26 penetrated.   The method for producing a heat conductive laminate according to any one of claims 26 to 28, wherein the insulating member has a heat conductive layer on a surface of the insulating layer.